Water can adsorb molecularly or dissociatively onto different sites of metal oxide surfaces. These adsorption sites can be disentangled using surface-sensitive vibrational spectroscopy. Here, we model Vibrational Sum Frequency (VSF) spectra for various forms of dissociated, deuterated water on a reconstructed, Al-terminated α-Al2O3(0001) surface at submonolayer coverages (the so-called 1-2, 1-4, and 1-4′ modes). Using an efficient scheme based on velocity-velocity autocorrelation functions, we go beyond previous normal mode analyses by including anharmonicity, mode coupling, and thermal surface motion in the framework of ab initio molecular dynamics. In this way, we calculate vibrational density of states curves, infrared, and VSF spectra. Comparing computed VSF spectra with measured ones, we find that relative frequencies of resonances are in quite good agreement and linewidths are reasonably well represented, while VSF intensities coincide not well. We argue that intensities are sensitively affected by local interactions and thermal fluctuations, even at such low coverage, while absolute peak positions strongly depend on the choice of the electronic structure method and on the appropriate inclusion of anharmonicity.
Skip Nav Destination
Article navigation
28 June 2019
Research Article|
June 24 2019
Vibrational spectra of dissociatively adsorbed D2O on Al-terminated -Al2O3(0001) surfaces from ab initio molecular dynamics
Giacomo Melani
;
Giacomo Melani
1
Theoretische Chemie, Institut für Chemie, Universität Potsdam
, Karl-Liebknecht-Straße 24-25, D-14476 Potsdam-Golm, Germany
Search for other works by this author on:
Yuki Nagata
;
Yuki Nagata
2
Max-Planck-Institut für Polymerforschung
, Ackermannweg 10, 55128 Mainz, Germany
Search for other works by this author on:
R. Kramer Campen
;
R. Kramer Campen
3
Fritz-Haber-Institut der Max-Planck-Gesellschaft
, Faradayweg 4-6, D-14195 Berlin, Germany
Search for other works by this author on:
Peter Saalfrank
Peter Saalfrank
a)
1
Theoretische Chemie, Institut für Chemie, Universität Potsdam
, Karl-Liebknecht-Straße 24-25, D-14476 Potsdam-Golm, Germany
Search for other works by this author on:
a)
Electronic mail: [email protected]
J. Chem. Phys. 150, 244701 (2019)
Article history
Received:
April 12 2019
Accepted:
May 23 2019
Citation
Giacomo Melani, Yuki Nagata, R. Kramer Campen, Peter Saalfrank; Vibrational spectra of dissociatively adsorbed D2O on Al-terminated -Al2O3(0001) surfaces from ab initio molecular dynamics. J. Chem. Phys. 28 June 2019; 150 (24): 244701. https://doi.org/10.1063/1.5099895
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Dielectric profile at the Pt(111)/water interface
Jia-Xin Zhu, Jun Cheng, et al.
Related Content
Vibrational spectroscopy of hydroxylated α -Al2O3(0001) surfaces with and without water: An ab initio molecular dynamics study
J. Chem. Phys. (July 2018)
Toward ab initio molecular dynamics modeling for sum-frequency generation spectra; an efficient algorithm based on surface-specific velocity-velocity correlation function
J. Chem. Phys. (September 2015)
Existence of weakly interacting OH bond at air/water interface
J. Chem. Phys. (April 2020)
Measurements and model of UV-induced oxidation of aluminum
J. Vac. Sci. Technol. A (March 2023)